The application of Mg-based electrochemical energy storage materials in high performance supercapacitors is an essential step to promote the exploitation and utilization of magnesium resources in the field of energy s...The application of Mg-based electrochemical energy storage materials in high performance supercapacitors is an essential step to promote the exploitation and utilization of magnesium resources in the field of energy storage.Unfortunately,the inherent chemical properties of magnesium lead to poor cycling stability and electrochemical reactivity,which seriously limit the application of Mg-based materials in supercapacitors.Herein,in this review,more than 70 research papers published in recent 10 years were collected and analyzed.Some representative research works were selected,and the results of various regulative strategies to improve the electrochemical performance of Mg-based materials were discussed.The effects of various regulative strategies(such as constructing nanostructures,synthesizing composites,defect engineering,and binder-free synthesis,etc.)on the electrochemical performance and their mechanism are demonstrated using spinelstructured MgX_(2)O_(4) and layered structured Mg-X-LDHs as examples.In addition,the application of magnesium oxide and magnesium hydroxide in electrode materials,MXene's solid spacers and hard templates are introduced.Finally,the challenges and outlooks of Mg-based electrochemical energy storage materials in high performance supercapacitors are also discussed.展开更多
Lost circulation is a common downhole problem of drilling in geothermal and high-temperature,high-pressure(HTHP)formations.Lost circulation material(LCM)is a regular preventive and remedial measure for lost circulatio...Lost circulation is a common downhole problem of drilling in geothermal and high-temperature,high-pressure(HTHP)formations.Lost circulation material(LCM)is a regular preventive and remedial measure for lost circulation.However,conventional LCMs seem ineffective in high-temperature formations.This may be due to the changes in the mechanical properties of LCMs and their sealing performance under high-temperature conditions.To understand how high temperature affects the fracture sealing performance of LCMs,we developed a coupled computational fluid dynamics-discrete element method(CFD-DEM)model to simulate the behavior of granular LCMs in fractures.We summarized the literature on the effects of high temperature on the mechanical properties of LCMs and the rheological properties of drilling fluid.We conducted sensitivity analyses to investigate how changing LCM slurry properties affected the fracture sealing efficiency at increasing temperatures.The results show that high temperature reduces the size,strength,and friction coefficient of LCMs as well as the drilling fluid viscosity.Smaller,softer,and less frictional LCM particles have lower bridging probability and slower bridging initiation.Smaller particles tend to form dual-particle bridges rather than single-particle bridges.These result in a deeper,tighter,but unstable sealing zone.Reduced drilling fluid viscosity leads to faster and shallower sealing zones.展开更多
Two-mm thick A1050 pure aluminum plates were successfully joined by conventional and rapid cooling friction stir welding(FSW), respectively. The microstructure and mechanical properties of the welded joints were inves...Two-mm thick A1050 pure aluminum plates were successfully joined by conventional and rapid cooling friction stir welding(FSW), respectively. The microstructure and mechanical properties of the welded joints were investigated by electron backscatter diffraction characterization, Vickers hardness measurements, and tensile testing. The results showed that liquid CO_(2) coolant significantly reduced the peak temperature and increased the cooling rate, so the rapidly cooled FSW joint exhibited fine grains with a large number of dislocations. The grain refinement mechanism of the FSW A1050 pure aluminum joint was primarily attributed to the combined effects of continuous dynamic recrystallization, grain subdivision, and geometric dynamic recrystallization. Compared with conventional FSW, the yield strength, ultimate tensile strength, and fracture elongation of rapidly cooled FSW joint were significantly enhanced, and the welding efficiency was increased from 80% to 93%. The enhanced mechanical properties and improved synergy of strength and ductility were obtained due to the increased dislocation density and remarkable grain refinement. The wear of the tool can produce several WC particles retained in the joint, and the contribution of second phase strengthening to the enhanced strength should not be ignored.展开更多
This work studied the microstructure,mechanical properties and damping properties of Mg_(95.34)Ni_(2)Y_(2.66) and Mg_(95.34)Zn_(1)Ni_(1)Y_(2.66)alloys systematically.The difference in the evolution of the long-period ...This work studied the microstructure,mechanical properties and damping properties of Mg_(95.34)Ni_(2)Y_(2.66) and Mg_(95.34)Zn_(1)Ni_(1)Y_(2.66)alloys systematically.The difference in the evolution of the long-period stacked ordered(LPSO)phase in the two alloys during heat treatment was the focus.The morphology of the as-cast Mg_(95.34)Ni_(2)Y_(2.66)presented a disordered network.After heat treatment at 773 K for 2 hours,the eutectic phase was integrated into the matrix,and the LPSO phase maintained the 18R structure.As Zn partially replaced Ni,the crystal grains became rounded in the cast alloy,and lamellar LPSO phases and more solid solution atoms were contained in the matrix after heat treatment of the Mg_(95.34)Zn_(1)Ni_(1)Y_(2.66)alloy.Both Zn and the heat treatment had a significant effect on damping.Obvious dislocation internal friction peaks and grain boundary internal friction peaks were found after temperature-dependent damping of the Mg_(95.34)Ni_(2)Y_(2.66)and Mg_(95.34)Zn_(1)Ni_(1)Y_(2.66)alloys.After heat treatment,the dislocation peak was significantly increased,especially in the alloy Mg_(95.34)Ni_(2)Y_(2).66.The annealed Mg_(95.34)Ni_(2)Y_(2.66)alloy with a rod-shaped LPSO phase exhibited a good damping performance of 0.14 atε=10^(−3),which was due to the difference between the second phase and solid solution atom content.These factors also affected the dynamic modulus of the alloy.The results of this study will help in further development of high-damping magnesium alloys.展开更多
Mn-rich LiFe_(1-x)Mn_(x)PO_(4)(x>0.5),which combines the high operation voltage of LiMnPO_(4)with excellent rate performa nce of LiFePO4,is hindered by its sluggish kinetic properties.Herein,thermodynamic equilibri...Mn-rich LiFe_(1-x)Mn_(x)PO_(4)(x>0.5),which combines the high operation voltage of LiMnPO_(4)with excellent rate performa nce of LiFePO4,is hindered by its sluggish kinetic properties.Herein,thermodynamic equilibrium analysis of Mn^(2+)-Fe^(2+)-Mg^(2+)-C_(2)O_(4)^(2-)-H_(2)O system is used to guide the design and preparation of insitu Mg-doped(Fe_(0.4)Mn_(0.6))_(1-x)Mg_(x)C_(2)O_(4)intermediate,which is then employed as an innovative precursor to synthesize high-performance Mg-doped LiFe_(0.4)Mn_(0.6)PO_(4).It indicates that the metal ions with a high precipitation efficiency and the stoichiometric precursors with uniform element distribution can be achieved under the optimized thermodynamic conditions.Meanwhile,accelerated Li+diffusivity and reduced charge transfer resistance originating from Mg doping are verified by various kinetic characterizations.Benefiting from the contributions of inherited homogeneous element distribution,small particle size,uniform carbon layer coating,enhanced Li+migration ability and structural stability induced by Mg doping,the Li(Fe_(0.4)Mn_(0.6))_(0.97)Mg_(0.03)PO_(4)/C exhibits splendid electrochemical performance.展开更多
Lead iodide(PbI2) is a vital raw material for preparing perovskite solar cells(PSCs),and it not only takes part in forming the light absorption layer but also remains in the grain boundary as a passivator.In other wor...Lead iodide(PbI2) is a vital raw material for preparing perovskite solar cells(PSCs),and it not only takes part in forming the light absorption layer but also remains in the grain boundary as a passivator.In other words,the PbI2 content in the precursor and as formed film will affect the efficiency and stability of the PSCs.With moderate residual PbI2,it passivates the bulk/surface defects of perovskite,reduces the interfacial recombination,promotes the perovskite stability,minimizes the device hysteresis,and so on.Deficient PbI2 residue will reduce the interfacial passivation effect and device performance.In addition to facilitating the non-radiative recombination,over PbI2 residue can also lead to electronic insulation in the grain boundary and deteriorate the device performance.However,the impact and regulation of PbI2 residue on the device performance and stability is still not fully understood.Herein,a comprehensive and detailed review is presented by discussing the PbI2 residue impact and its regulation strategies(i.e., elimination,facilitation and conversion of the residue PbI2) to manipulate the PbI2 content,distribution and forms.Finally,we also show future outlooks in this field,with an aim to help further the progression of high-efficiency and stable PSCs.展开更多
The use of fillers to enhance the corrosion protection of epoxy resins has been widely applied.In this work,cerium dioxide(CeO_(2))and benzotriazole(BTA)were introduced into an epoxy resin to enhance the corrosion res...The use of fillers to enhance the corrosion protection of epoxy resins has been widely applied.In this work,cerium dioxide(CeO_(2))and benzotriazole(BTA)were introduced into an epoxy resin to enhance the corrosion resistance of Q235 carbon steel.Scanning electron microscopy results indicated that the CeO_(2) grains were rod-like and ellipsoidal in shape,and the distribution pattern of BTA was analyzed by energy dispersive spectroscope.The dynamic potential polarization curve proved the excellent corrosion resistance of the composite epoxy resin with CeO_(2) and BTA co-addition,and electrochemical impedance spectroscopy test analysis indicated the significantly enhanced long-term corrosion protection performance of the composite coating.And the optimal protective performance was provided by the coating containing 0.3%(mass)CeO_(2) and 20%(mass)BTA,which was attributed to the barrier performance of CeO_(2) particles and the chemical barrier effect of BTA.The formation of corrosion products was analyzed using X-ray diffraction.In addition,the corrosion resistance mechanism of the coating was also discussed in detail.展开更多
Water-quenched copper-nickel metallurgical slag enriched with olivine minerals exhibits promising potential for the production of CO_(2)-mineralized cementitious materials.In this work,copper-nickel slag-based cementi...Water-quenched copper-nickel metallurgical slag enriched with olivine minerals exhibits promising potential for the production of CO_(2)-mineralized cementitious materials.In this work,copper-nickel slag-based cementitious material(CNCM)was synthesized by using different chemical activation methods to enhance its hydration reactivity and CO_(2) mineralization capacity.Different water curing ages and carbonation conditions were explored related to their carbonation and mechanical properties development.Meanwhile,thermogravimetry differential scanning calorimetry and X-ray diffraction methods were applied to evaluate the CO_(2) adsorption amount and carbonation products of CNCM.Microstructure development of carbonated CNCM blocks was examined by backscattered electron imaging(BSE)with energy-dispersive X-ray spectrometry.Results showed that among the studied samples,the CNCM sample that was subjected to water curing for 3 d exhibited the highest CO_(2) sequestration amount of 8.51wt%at 80℃and 72 h while presenting the compressive strength of 39.07 MPa.This result indicated that 1 t of this CNCM can sequester 85.1 kg of CO_(2) and exhibit high compressive strength.Although the addition of citric acid did not improve strength development,it was beneficial to increase the CO_(2) diffusion and adsorption amount under the same carbonation conditions from BSE results.This work provides guidance for synthesizing CO_(2)-mineralized cementitious materials using large amounts of metallurgical slags containing olivine minerals.展开更多
Solid oxide fuel cells(SOFCs)have attracted a great deal of interest because they have the highest efficiency without using any noble metal as catalysts among all the fuel cell technologies.However,traditional SOFCs s...Solid oxide fuel cells(SOFCs)have attracted a great deal of interest because they have the highest efficiency without using any noble metal as catalysts among all the fuel cell technologies.However,traditional SOFCs suffer from having a higher volume,current leakage,complex connections,and difficulty in gas sealing.To solve these problems,Rolls-Royce has fabricated a simple design by stacking cells in series on an insulating porous support,resulting in the tubular segmented-in-series solid oxide fuel cells(SIS-SOFCs),which achieved higher output voltage.This work systematically reviews recent advances in the structures,preparation methods,perform-ances,and stability of tubular SIS-SOFCs in experimental and numerical studies.Finally,the challenges and future development of tubular SIS-SOFCs are also discussed.The findings of this work can help guide the direction and inspire innovation of future development in this field.展开更多
The development of anode materials with high rate capability and long charge-discharge plateau is the key to improve per-formance of lithium-ion capacitors(LICs).Herein,the porous graphitic carbon(PGC-1300)derived fro...The development of anode materials with high rate capability and long charge-discharge plateau is the key to improve per-formance of lithium-ion capacitors(LICs).Herein,the porous graphitic carbon(PGC-1300)derived from a new triply interpenetrated co-balt metal-organic framework(Co-MOF)was prepared through the facile and robust carbonization at 1300°C and washing by HCl solu-tion.The as-prepared PGC-1300 featured an optimized graphitization degree and porous framework,which not only contributes to high plateau capacity(105.0 mAh·g^(−1)below 0.2 V at 0.05 A·g^(−1)),but also supplies more convenient pathways for ions and increases the rate capability(128.5 mAh·g^(−1)at 3.2 A·g^(−1)).According to the kinetics analyses,it can be found that diffusion regulated surface induced capa-citive process and Li-ions intercalation process are coexisted for lithium-ion storage.Additionally,LIC PGC-1300//AC constructed with pre-lithiated PGC-1300 anode and activated carbon(AC)cathode exhibited an increased energy density of 102.8 Wh·kg^(−1),a power dens-ity of 6017.1 W·kg^(−1),together with the excellent cyclic stability(91.6%retention after 10000 cycles at 1.0 A·g^(−1)).展开更多
The retarding effect of protein retarder on phosphorus building gypsum(PBG)and desulfurization building gypsum(DBG)was investigated,and the results show that protein retarder for DBG can effectively prolong the settin...The retarding effect of protein retarder on phosphorus building gypsum(PBG)and desulfurization building gypsum(DBG)was investigated,and the results show that protein retarder for DBG can effectively prolong the setting time and displays a better retarding effect,but for PBG shows a poor retarding effect.Furthermore,the deterioration reason of the retarding effect of protein retarder on PBG was investigated by measuring the pH value and the retarder concentration of the liquid phase from vacuum filtration of PBG slurry at different hydration time,and the measure to improve the retarding effect of protein retarding on PBG was suggested.The pH value of PBG slurry(<5.0)is lower than that of DBG slurry(7.8-8.5).After hydration for 5 min,the concentration of retarder in liquid phase of DBG slurry gradually decreases,but in liquid phase of PBG slurry continually increases,which results in the worse retarding effect of protein retarder on PBG.The liquid phase pH value of PBG slurry can be adjusted higher by sodium silicate,which is beneficial to improvement in the retarding effect of the retarder.By adding 1.0%of sodium silicate,the initial setting time of PBG was efficiently prolonged from 17 to 210 min,but little effect on the absolute dry flexural strength was observed.展开更多
Hot torsion tests for AZ80 magnesium alloy were carried out in the temperature range of 380℃-260℃,with a constant decreasing temperature rate of 10℃/s in order to weaken the basal texture and refine the grains.The ...Hot torsion tests for AZ80 magnesium alloy were carried out in the temperature range of 380℃-260℃,with a constant decreasing temperature rate of 10℃/s in order to weaken the basal texture and refine the grains.The results indicated that the average grain sizes were refined forming gradient structure with increasing specimen radial position from center(12.2-5.4μm),and that the initial basal texture intensity of the extruded magnesium alloy was weakened from 46.2 to 8.3.Furthermore,the extension twins(ETs)could be disintegrated from the twins forming separated twins with smaller sizes.Interestingly,ETs with the same twin variant intersecting with each other could be coalesced forming grains with similar orientation,while ETs with different twin variants were separated by twins boundaries contributing to grain refinement.Moreover,in addition to the conventional continuous dynamic recrystallized(CDRX)grains with 30˚orientation rotated around C-axis of the parent grains,CDRXed grains with 30˚rotation around a-axis and random rotation axis were also discerned.Besides,the CDRX evolution induced twins were also elaborated,exhibiting the complex competition between CDRX and twining.Hot torsion deformation with constant decreasing temperatures rate is an effective way of grain refinement and texture modification.展开更多
RuO_(2) has been considered a potential alternative to commercial IrO_(2) for the oxygen evolution reaction(OER)due to its superior intrinsic activity.However,its inherent structure dissolution in acidic environments ...RuO_(2) has been considered a potential alternative to commercial IrO_(2) for the oxygen evolution reaction(OER)due to its superior intrinsic activity.However,its inherent structure dissolution in acidic environments restricts its commercial applications.In this study,we report a novel Pd-doped ruthenium oxide(Pd–RuO_(2))nanosheet catalyst that exhibits improved activity and stability through a synergistic effect of Pd modulation of Ru electronic structure and the two-dimensional structure.The catalyst exhibits excellent performance,achieving an overpotential of only 204 mVat a current density of 10 mA cm^(-2).Impressively,after undergoing 8000 cycles of cyclic voltammetry testing,the overpotential merely decreased by 5 mV.The PEM electrolyzer with Pd0.08Ru0.92O_(2) as an anode catalyst survived an almost 130 h operation at 200 mA cm^(-2).To elucidate the underlying mechanisms responsible for the enhanced stability,we conducted an X-ray photoelectron spectroscopy(XPS)analysis,which reveals that the electron transfer from Pd to Ru effectively circumvents the over-oxidation of Ru,thus playing a crucial role in enhancing the catalyst's stability.Furthermore,density functional theory(DFT)calculations provide compelling evidence that the introduction of Pd into RuO_(2) effectively modulates electron correlations and facilitates the electron transfer from Pd to Ru,thereby preventing the overoxidation of Ru.Additionally,the application of the two-dimensional structure effectively inhibited the aggregation and growth of nanoparticles,further bolstering the structural integrity of the catalyst.展开更多
The purpose of this research is to investigate the hydration behavior and cementitious properties of the mixture of calcium carbonate and aluminate, and to explore whether it can be adopted as a new low-carbon cementi...The purpose of this research is to investigate the hydration behavior and cementitious properties of the mixture of calcium carbonate and aluminate, and to explore whether it can be adopted as a new low-carbon cementitious material. The composite system of calcium carbonate and aluminate minerals is studied by measuring the component of hydration products, the hydration heat, setting time and compressive strength.The results prove that the composite system has certain cementitious properties and is feasible to prepare new low-carbon cement.展开更多
High-temperature oxidation behavior of ferrovanadium(FeV_(2)O_(4))and ferrochrome(FeCr_(2)O_(4))spinels is crucial for the application of spinel as an energy material,as well as for the clean usage of high-chromium va...High-temperature oxidation behavior of ferrovanadium(FeV_(2)O_(4))and ferrochrome(FeCr_(2)O_(4))spinels is crucial for the application of spinel as an energy material,as well as for the clean usage of high-chromium vanadium slag.Herein,the nonisothermal oxidation behavior of FeV_(2)O_(4)and FeCr_(2)O_(4)prepared by high-temperature solid-state reaction was examined by thermogravimetry and X-ray diffraction(XRD)at heating rates of 5,10,and 15 K/min.The apparent activation energy was determined by the Kissinger-Akahira-Sunose(KAS)method,whereas the mechanism function was elucidated by the Malek method.Moreover,in-situ XRD was conducted to deduce the phase transformation of the oxidation mechanism for FeV_(2)O_(4)and FeCr_(2)O_(4).The results reveal a gradual increase in the overall apparent activation energies for FeV_(2)O_(4)and FeCr_(2)O_(4)during oxidation.Four stages of the oxidation process are observed based on the oxidation conversion rate of each compound.The oxidation mechanisms of FeV_(2)O_(4)and FeCr_(2)O_(4)are complex and have distinct mechanisms.In particular,the chemical reaction controls the entire oxidation process for FeV_(2)O_(4),whereas that for FeCr_(2)O_(4)transitions from a three-dimensional diffusion model to a chemical reaction model.According to the in-situ XRD results,numerous intermediate products are observed during the oxidation process of both compounds,eventually resulting in the final products FeVO_(4)and V2O_(5)for FeV_(2)O_(4)and Fe_(2)O_(3)and Cr_(2)O_(3)for FeCr_(2)O_(4),respectively.展开更多
Combination of CO_(2) capture using inorganic alkali with subsequently electrochemical conversion of the resultant HCO_(3)^(-)to high-value chemicals is a promising route of low cost and high efficiency.The electroche...Combination of CO_(2) capture using inorganic alkali with subsequently electrochemical conversion of the resultant HCO_(3)^(-)to high-value chemicals is a promising route of low cost and high efficiency.The electrochemical reduction of HCO_(3)^(-)is challenging due to the inaccessible of negatively charged molecular groups to the electrode surface.Herein,we adopt a comprehensive strategy to tackle this challenge,i.e.,cascade of in situ chemical conversion of HCO_(3)^(-)to CO_(2) and CO_(2) electrochemical reduction in a flow cell.With a tailored Ni-N-S single atom catalyst(SACs),where sulfur(S)atoms located in the second shell of Ni center,the CO_(2)electroreduction(CO_(2)ER)to CO is boosted.The experimental results and density functional theory(DFT)calculations reveal that the introduction of S increases the p electron density of N atoms near Ni atom,thereby stabilizing^(*)H over N and boosting the first proton coupled electron transfer process of CO_(2)ER,i.e.,^(*)+e^(-)+^(*)H+^(*)CO_(2)→^(*)COOH.As a result,the obtained catalyst exhibits a high faradaic efficiency(FE_(CO)~98%)and a low overpotential of 425 mV for CO production as well as a superior turnover frequency(TOF)of 47397 h^(-1),outcompeting most of the reported Ni SACs.More importantly,an extremely high FECOof 90%is achieved at 50 mA cm^(-2)in the designed membrane electrode assembly(MEA)cascade electrolyzer fed with liquid bicarbonate.This work not only highlights the significant role of the second coordination on the first coordination shell of the central metal for CO_(2)ER,but also provides an alternative and feasible strategy to realize the electrochemical conversion of HCO_(3)^(-)to high-value chemicals.展开更多
Mg-based amorphous alloys exhibit efficient catalytic performance and excellent biocompatibility with a promising application probability,specifically in the field of azo dye wastewater degradation.However,the problem...Mg-based amorphous alloys exhibit efficient catalytic performance and excellent biocompatibility with a promising application probability,specifically in the field of azo dye wastewater degradation.However,the problems like difficulty in preparation and poor cycling stability need to be solved.At present,Mg-based amorphous alloys applied in wastewater degradation are available in powder and ribbon.The amorphous alloy powder fabricated by ball milling has a high specific surface area,and its reactivity is thousands of times better than that of gas atomized alloy powder.But the development is limited due to the high energy consumption,difficult and costly process of powder recycling.The single roller melt-spinning method is a new manufacturing process of amorphous alloy ribbon.Compared to amorphous powder,the specific surface area of amorphous ribbon is relatively lower,therefore,it is necessary to carry out surface modification to enhance it.Dealloying is a way that can form a pore structure on the surface of the amorphous alloys,increasing the specific surface area and providing more reactive sites,which all contribute to the catalytic performance.Exploring the optimal conditions for Mg-based amorphous alloys in wastewater degradation by adjusting amorphous alloy composition,choosing suitable method to preparation and surface modification,reducing cost,expanding the pH range will advance the steps to put Mg-based amorphous alloys in industrial environments into practice.展开更多
Although metallic rhodium(Rh)is regarded as a promising platinum-alternative anode catalyst of direct methanol fuel cell(DMFC),the conventional"particle-to-face"contact model between Rh and matrix largely li...Although metallic rhodium(Rh)is regarded as a promising platinum-alternative anode catalyst of direct methanol fuel cell(DMFC),the conventional"particle-to-face"contact model between Rh and matrix largely limits the overall electrocatalytic performance due to their insufficient cooperative effects.Herein,we report a controllable and robust heterointerface engineering strategy for the bottom-up fabrication of rhombic Rh nanosheets in situ confined on Ti_3C_(2)T_x MXene nanolamellas(Rh NS/MXene)via a convenient stereoassembly process.This unique design concept gives the resulting 2D/2D Rh NS/MXene heterostructure intriguing textural features,including large accessible surface areas,strong"face-toface"interfacial interactions,homogeneous Rh nanosheet distribution,ameliorative electronic structure,and high electronic conductivity.As a consequence,the as-prepared Rh NS/MXene nanoarchitectures exhibit exceptional electrocatalytic methanol oxidation properties in terms of a large electrochemically active surface area of 126.2 m~2 g_(Rh)~(-1),a high mass activity of 1056.9 mA mg_(Rh)-~1,and a long service life,which significantly outperform those of conventional particle-shaped Rh catalysts supported by carbon black,carbon nanotubes,reduced graphene oxide,and MXene matrixes as well as the commercial Pt nanoparticle/carbon black and Pd nanoparticle/carbon black catalysts with the same noble metal loading amount.Density functional theory calculations further demonstrate that the direct electronic interaction at the well-contacted 2D/2D heterointerfaces effectively enhances the adsorption energy of Rh nanosheets and induces a left shift of the d-band center,thereby making the Rh NS/MXene configuration suffer less from CO poisoning.This work highlights the importance of rational heterointerface design in the construction of advanced noble metal/MXene electrocatalysts,which may provide new avenues for developing the next-generation DMFC devices.展开更多
The extruded AZ80+0.4%Ce magnesium alloy was twisted in the temperature range of 300-380℃by using a Gleeble 3500 thermal simulation test machine with a torsion unit.The deformed cylindrical specimens were cooled at a...The extruded AZ80+0.4%Ce magnesium alloy was twisted in the temperature range of 300-380℃by using a Gleeble 3500 thermal simulation test machine with a torsion unit.The deformed cylindrical specimens were cooled at a cooling rate of 10℃/s or 0.1℃/s,respectively,and aged at 170℃.The microstructure analysis results showed that the grain size decreased with increasing specimen radial position from center(SRPC),and that the strong initial basal texture of the extruded magnesium alloy was weakened.Both continuous and discontinuous dynamic recrystallization mechanisms were involved in contributing to the grain refinement for all specimens investigated.And a novel extension twinning induced dynamic recrystallization mechanism was proposed for specimen deformed at 300℃.For the specimens deformed at 300℃and 340℃followed by a slow cooling rate(0.1℃/s),precipitates of various shapes(β-Mg_(17)Al_(12)),with the dominant precipitates being on the grains boundaries,appeared on the surface section.For specimen deformed at 380℃,lamellar precipitates(LPS)in the interiors of the grains were predominant.After aging,the LPS still dominated for specimens twisted at 380℃;however,the LPS gradually decreased with decreasing deformation temperatures from 380℃to 300℃.Dynamically precipitatedβ,especially those decorating the grain boundaries,changed the competition pictures for the LPS and precipitates of other shapes after aging.Interestingly,LPS dominated the areas for the center section of the specimens after aging regardless of deformation temperatures.Low temperature deformation with high SRPC followed by rapid cooling rate increased the micro hardness of the alloy after aging due to refined grain,reduced precipitates size,decreased lamellar spacing as well as strain hardening.展开更多
Hydrogen evolution reaction(HER)has become a key factor affecting the cycling stability of aqueous Zn-ion batteries,while the corresponding fundamental issues involving HER are still unclear.Herein,the reaction mechan...Hydrogen evolution reaction(HER)has become a key factor affecting the cycling stability of aqueous Zn-ion batteries,while the corresponding fundamental issues involving HER are still unclear.Herein,the reaction mechanisms of HER on various crystalline surfaces have been investigated by first-principle calculations based on density functional theory.It is found that the Volmer step is the ratelimiting step of HER on the Zn(002)and(100)surfaces,while,the reaction rates of HER on the Zn(101),(102)and(103)surfaces are determined by the Tafel step.Moreover,the correlation between HER activity and the generalized coordination number(CN)of Zn at the surfaces has been revealed.The relatively weaker HER activity on Zn(002)surface can be attributed to the higher CN of surface Zn atom.The atomically uneven Zn(002)surface shows significantly higher HER activity than the flat Zn(002)surface as the CN of the surface Zn atom is lowered.The CN of surface Zn atom is proposed as a key descriptor of HER activity.Tuning the CN of surface Zn atom would be a vital strategy to inhibit HER on the Zn anode surface based on the presented theoretical studies.Furthermore,this work provides a theoretical basis for the in-depth understanding of HER on the Zn surface.展开更多
基金financial support provided by Projects(no.2020CDJXZ001)the Fundamental Research Funds for the Central Universities+1 种基金the Technology Innovation and Application Development Special Project of Chongqing(Z20211350 and Z20211351)Scientific Research Project of Chongqing Ecological Environment Bureau(no.CQEE2022-STHBZZ118)。
文摘The application of Mg-based electrochemical energy storage materials in high performance supercapacitors is an essential step to promote the exploitation and utilization of magnesium resources in the field of energy storage.Unfortunately,the inherent chemical properties of magnesium lead to poor cycling stability and electrochemical reactivity,which seriously limit the application of Mg-based materials in supercapacitors.Herein,in this review,more than 70 research papers published in recent 10 years were collected and analyzed.Some representative research works were selected,and the results of various regulative strategies to improve the electrochemical performance of Mg-based materials were discussed.The effects of various regulative strategies(such as constructing nanostructures,synthesizing composites,defect engineering,and binder-free synthesis,etc.)on the electrochemical performance and their mechanism are demonstrated using spinelstructured MgX_(2)O_(4) and layered structured Mg-X-LDHs as examples.In addition,the application of magnesium oxide and magnesium hydroxide in electrode materials,MXene's solid spacers and hard templates are introduced.Finally,the challenges and outlooks of Mg-based electrochemical energy storage materials in high performance supercapacitors are also discussed.
基金The authors gratefully acknowledge the financial support from the National Natural Science Foundation of China(Grant No.52274009)China Postdoctoral Science Foundation(Grant No.2022M723501)Science and Technology Planning Project of Sichuan Province(Grant No.2021YJ0359).
文摘Lost circulation is a common downhole problem of drilling in geothermal and high-temperature,high-pressure(HTHP)formations.Lost circulation material(LCM)is a regular preventive and remedial measure for lost circulation.However,conventional LCMs seem ineffective in high-temperature formations.This may be due to the changes in the mechanical properties of LCMs and their sealing performance under high-temperature conditions.To understand how high temperature affects the fracture sealing performance of LCMs,we developed a coupled computational fluid dynamics-discrete element method(CFD-DEM)model to simulate the behavior of granular LCMs in fractures.We summarized the literature on the effects of high temperature on the mechanical properties of LCMs and the rheological properties of drilling fluid.We conducted sensitivity analyses to investigate how changing LCM slurry properties affected the fracture sealing efficiency at increasing temperatures.The results show that high temperature reduces the size,strength,and friction coefficient of LCMs as well as the drilling fluid viscosity.Smaller,softer,and less frictional LCM particles have lower bridging probability and slower bridging initiation.Smaller particles tend to form dual-particle bridges rather than single-particle bridges.These result in a deeper,tighter,but unstable sealing zone.Reduced drilling fluid viscosity leads to faster and shallower sealing zones.
基金Funded by the Natural Science Foundation of Jiangsu Province(No.BK20211067)“Qing Lan” Project of Jiangsu Province。
文摘Two-mm thick A1050 pure aluminum plates were successfully joined by conventional and rapid cooling friction stir welding(FSW), respectively. The microstructure and mechanical properties of the welded joints were investigated by electron backscatter diffraction characterization, Vickers hardness measurements, and tensile testing. The results showed that liquid CO_(2) coolant significantly reduced the peak temperature and increased the cooling rate, so the rapidly cooled FSW joint exhibited fine grains with a large number of dislocations. The grain refinement mechanism of the FSW A1050 pure aluminum joint was primarily attributed to the combined effects of continuous dynamic recrystallization, grain subdivision, and geometric dynamic recrystallization. Compared with conventional FSW, the yield strength, ultimate tensile strength, and fracture elongation of rapidly cooled FSW joint were significantly enhanced, and the welding efficiency was increased from 80% to 93%. The enhanced mechanical properties and improved synergy of strength and ductility were obtained due to the increased dislocation density and remarkable grain refinement. The wear of the tool can produce several WC particles retained in the joint, and the contribution of second phase strengthening to the enhanced strength should not be ignored.
基金funded by the National Natural Science Foundation of China(Nos.51801189)The Central Guidance on Local Science and Technology Development Fund of Shanxi Province(Nos.YDZJTSX2021A027)+2 种基金The National Natural Science Foundation of China(Nos.51801189)The Science and Technology Major Project of Shanxi Province(No.20191102008,20191102007)The North University of China Youth Academic Leader Project(No.11045505).
文摘This work studied the microstructure,mechanical properties and damping properties of Mg_(95.34)Ni_(2)Y_(2.66) and Mg_(95.34)Zn_(1)Ni_(1)Y_(2.66)alloys systematically.The difference in the evolution of the long-period stacked ordered(LPSO)phase in the two alloys during heat treatment was the focus.The morphology of the as-cast Mg_(95.34)Ni_(2)Y_(2.66)presented a disordered network.After heat treatment at 773 K for 2 hours,the eutectic phase was integrated into the matrix,and the LPSO phase maintained the 18R structure.As Zn partially replaced Ni,the crystal grains became rounded in the cast alloy,and lamellar LPSO phases and more solid solution atoms were contained in the matrix after heat treatment of the Mg_(95.34)Zn_(1)Ni_(1)Y_(2.66)alloy.Both Zn and the heat treatment had a significant effect on damping.Obvious dislocation internal friction peaks and grain boundary internal friction peaks were found after temperature-dependent damping of the Mg_(95.34)Ni_(2)Y_(2.66)and Mg_(95.34)Zn_(1)Ni_(1)Y_(2.66)alloys.After heat treatment,the dislocation peak was significantly increased,especially in the alloy Mg_(95.34)Ni_(2)Y_(2).66.The annealed Mg_(95.34)Ni_(2)Y_(2.66)alloy with a rod-shaped LPSO phase exhibited a good damping performance of 0.14 atε=10^(−3),which was due to the difference between the second phase and solid solution atom content.These factors also affected the dynamic modulus of the alloy.The results of this study will help in further development of high-damping magnesium alloys.
基金financially supported by the National Natural Science Foundation of China(No.51904250)the China Postdoctoral Science Foundation(No.2021M692254)+2 种基金the Sichuan Science and Technology Program(No.2022YFG0098)the Fundamental Research Funds for the Central Universities(Nos.2021CDSN-02,2022SCU12002,2022CDZG-17,2022CDSN-08,2022CDZG-9)the Hohhot Science and Technology Program(No.2023-Jie Bang Gua Shuai-Gao-3)。
文摘Mn-rich LiFe_(1-x)Mn_(x)PO_(4)(x>0.5),which combines the high operation voltage of LiMnPO_(4)with excellent rate performa nce of LiFePO4,is hindered by its sluggish kinetic properties.Herein,thermodynamic equilibrium analysis of Mn^(2+)-Fe^(2+)-Mg^(2+)-C_(2)O_(4)^(2-)-H_(2)O system is used to guide the design and preparation of insitu Mg-doped(Fe_(0.4)Mn_(0.6))_(1-x)Mg_(x)C_(2)O_(4)intermediate,which is then employed as an innovative precursor to synthesize high-performance Mg-doped LiFe_(0.4)Mn_(0.6)PO_(4).It indicates that the metal ions with a high precipitation efficiency and the stoichiometric precursors with uniform element distribution can be achieved under the optimized thermodynamic conditions.Meanwhile,accelerated Li+diffusivity and reduced charge transfer resistance originating from Mg doping are verified by various kinetic characterizations.Benefiting from the contributions of inherited homogeneous element distribution,small particle size,uniform carbon layer coating,enhanced Li+migration ability and structural stability induced by Mg doping,the Li(Fe_(0.4)Mn_(0.6))_(0.97)Mg_(0.03)PO_(4)/C exhibits splendid electrochemical performance.
基金financially supported by the National Natural Science Foundation of China(U21A2078,22179042,and 12104170)the Natural Science Foundation of Fujian Province(2020J06021 and 2020J01064)Scientific Research Funds of Huaqiao University(23BS109)。
文摘Lead iodide(PbI2) is a vital raw material for preparing perovskite solar cells(PSCs),and it not only takes part in forming the light absorption layer but also remains in the grain boundary as a passivator.In other words,the PbI2 content in the precursor and as formed film will affect the efficiency and stability of the PSCs.With moderate residual PbI2,it passivates the bulk/surface defects of perovskite,reduces the interfacial recombination,promotes the perovskite stability,minimizes the device hysteresis,and so on.Deficient PbI2 residue will reduce the interfacial passivation effect and device performance.In addition to facilitating the non-radiative recombination,over PbI2 residue can also lead to electronic insulation in the grain boundary and deteriorate the device performance.However,the impact and regulation of PbI2 residue on the device performance and stability is still not fully understood.Herein,a comprehensive and detailed review is presented by discussing the PbI2 residue impact and its regulation strategies(i.e., elimination,facilitation and conversion of the residue PbI2) to manipulate the PbI2 content,distribution and forms.Finally,we also show future outlooks in this field,with an aim to help further the progression of high-efficiency and stable PSCs.
基金financially supported by the National Natural Science Foundation of China(22178242)the Shanxi Provincial Key Research and Development Project(202102040201009).
文摘The use of fillers to enhance the corrosion protection of epoxy resins has been widely applied.In this work,cerium dioxide(CeO_(2))and benzotriazole(BTA)were introduced into an epoxy resin to enhance the corrosion resistance of Q235 carbon steel.Scanning electron microscopy results indicated that the CeO_(2) grains were rod-like and ellipsoidal in shape,and the distribution pattern of BTA was analyzed by energy dispersive spectroscope.The dynamic potential polarization curve proved the excellent corrosion resistance of the composite epoxy resin with CeO_(2) and BTA co-addition,and electrochemical impedance spectroscopy test analysis indicated the significantly enhanced long-term corrosion protection performance of the composite coating.And the optimal protective performance was provided by the coating containing 0.3%(mass)CeO_(2) and 20%(mass)BTA,which was attributed to the barrier performance of CeO_(2) particles and the chemical barrier effect of BTA.The formation of corrosion products was analyzed using X-ray diffraction.In addition,the corrosion resistance mechanism of the coating was also discussed in detail.
基金supported by the Intergovernmental International Science and Technology Innovation Cooperation Key Project of the National Key Research and Development Program of China (No.2022YFE0135100)the National Natural Science Foundation of China (No.52072171)+1 种基金the Beijing Nova Program (No.20220484057)the Priority Academic Program Development of Jiangsu Higher Education Institutions (PAPD).
文摘Water-quenched copper-nickel metallurgical slag enriched with olivine minerals exhibits promising potential for the production of CO_(2)-mineralized cementitious materials.In this work,copper-nickel slag-based cementitious material(CNCM)was synthesized by using different chemical activation methods to enhance its hydration reactivity and CO_(2) mineralization capacity.Different water curing ages and carbonation conditions were explored related to their carbonation and mechanical properties development.Meanwhile,thermogravimetry differential scanning calorimetry and X-ray diffraction methods were applied to evaluate the CO_(2) adsorption amount and carbonation products of CNCM.Microstructure development of carbonated CNCM blocks was examined by backscattered electron imaging(BSE)with energy-dispersive X-ray spectrometry.Results showed that among the studied samples,the CNCM sample that was subjected to water curing for 3 d exhibited the highest CO_(2) sequestration amount of 8.51wt%at 80℃and 72 h while presenting the compressive strength of 39.07 MPa.This result indicated that 1 t of this CNCM can sequester 85.1 kg of CO_(2) and exhibit high compressive strength.Although the addition of citric acid did not improve strength development,it was beneficial to increase the CO_(2) diffusion and adsorption amount under the same carbonation conditions from BSE results.This work provides guidance for synthesizing CO_(2)-mineralized cementitious materials using large amounts of metallurgical slags containing olivine minerals.
基金supported by the National Natural Science Foundation of China (Nos.21701083 and 22179054).
文摘Solid oxide fuel cells(SOFCs)have attracted a great deal of interest because they have the highest efficiency without using any noble metal as catalysts among all the fuel cell technologies.However,traditional SOFCs suffer from having a higher volume,current leakage,complex connections,and difficulty in gas sealing.To solve these problems,Rolls-Royce has fabricated a simple design by stacking cells in series on an insulating porous support,resulting in the tubular segmented-in-series solid oxide fuel cells(SIS-SOFCs),which achieved higher output voltage.This work systematically reviews recent advances in the structures,preparation methods,perform-ances,and stability of tubular SIS-SOFCs in experimental and numerical studies.Finally,the challenges and future development of tubular SIS-SOFCs are also discussed.The findings of this work can help guide the direction and inspire innovation of future development in this field.
基金the National Natural Science Foundation of China(No.52004179)the Natural Nat-ural Science Foundation of Guangxi Province,China(No.2020GXNSFAA159015)Shanxi Water and Wood New Carbon Materials Technology Co.,Ltd.,China,and Shanxi Wote Haimer New Materials Technology Co.,Ltd,China.
文摘The development of anode materials with high rate capability and long charge-discharge plateau is the key to improve per-formance of lithium-ion capacitors(LICs).Herein,the porous graphitic carbon(PGC-1300)derived from a new triply interpenetrated co-balt metal-organic framework(Co-MOF)was prepared through the facile and robust carbonization at 1300°C and washing by HCl solu-tion.The as-prepared PGC-1300 featured an optimized graphitization degree and porous framework,which not only contributes to high plateau capacity(105.0 mAh·g^(−1)below 0.2 V at 0.05 A·g^(−1)),but also supplies more convenient pathways for ions and increases the rate capability(128.5 mAh·g^(−1)at 3.2 A·g^(−1)).According to the kinetics analyses,it can be found that diffusion regulated surface induced capa-citive process and Li-ions intercalation process are coexisted for lithium-ion storage.Additionally,LIC PGC-1300//AC constructed with pre-lithiated PGC-1300 anode and activated carbon(AC)cathode exhibited an increased energy density of 102.8 Wh·kg^(−1),a power dens-ity of 6017.1 W·kg^(−1),together with the excellent cyclic stability(91.6%retention after 10000 cycles at 1.0 A·g^(−1)).
文摘The retarding effect of protein retarder on phosphorus building gypsum(PBG)and desulfurization building gypsum(DBG)was investigated,and the results show that protein retarder for DBG can effectively prolong the setting time and displays a better retarding effect,but for PBG shows a poor retarding effect.Furthermore,the deterioration reason of the retarding effect of protein retarder on PBG was investigated by measuring the pH value and the retarder concentration of the liquid phase from vacuum filtration of PBG slurry at different hydration time,and the measure to improve the retarding effect of protein retarding on PBG was suggested.The pH value of PBG slurry(<5.0)is lower than that of DBG slurry(7.8-8.5).After hydration for 5 min,the concentration of retarder in liquid phase of DBG slurry gradually decreases,but in liquid phase of PBG slurry continually increases,which results in the worse retarding effect of protein retarder on PBG.The liquid phase pH value of PBG slurry can be adjusted higher by sodium silicate,which is beneficial to improvement in the retarding effect of the retarder.By adding 1.0%of sodium silicate,the initial setting time of PBG was efficiently prolonged from 17 to 210 min,but little effect on the absolute dry flexural strength was observed.
基金supported by key technology research and development project of ShanXi province(20201102019)Natural science foundation of Shanxi Province(201901D111167)+2 种基金Shanxi Scholarship Council of China(2020-117)JCKY2018408B003Magnesium alloy high-performance XXX multi-directional extrusion technologyXX supporting scientific research project(xxxx-2019-021).
文摘Hot torsion tests for AZ80 magnesium alloy were carried out in the temperature range of 380℃-260℃,with a constant decreasing temperature rate of 10℃/s in order to weaken the basal texture and refine the grains.The results indicated that the average grain sizes were refined forming gradient structure with increasing specimen radial position from center(12.2-5.4μm),and that the initial basal texture intensity of the extruded magnesium alloy was weakened from 46.2 to 8.3.Furthermore,the extension twins(ETs)could be disintegrated from the twins forming separated twins with smaller sizes.Interestingly,ETs with the same twin variant intersecting with each other could be coalesced forming grains with similar orientation,while ETs with different twin variants were separated by twins boundaries contributing to grain refinement.Moreover,in addition to the conventional continuous dynamic recrystallized(CDRX)grains with 30˚orientation rotated around C-axis of the parent grains,CDRXed grains with 30˚rotation around a-axis and random rotation axis were also discerned.Besides,the CDRX evolution induced twins were also elaborated,exhibiting the complex competition between CDRX and twining.Hot torsion deformation with constant decreasing temperatures rate is an effective way of grain refinement and texture modification.
基金supported by the National Natural Science Foundation of China(No.22209035)the Major Science and Technology Projects of Yunnan Province(No.202302AH360001)the Natural Science Foundation of Hebei Province(No.E2020202091).
文摘RuO_(2) has been considered a potential alternative to commercial IrO_(2) for the oxygen evolution reaction(OER)due to its superior intrinsic activity.However,its inherent structure dissolution in acidic environments restricts its commercial applications.In this study,we report a novel Pd-doped ruthenium oxide(Pd–RuO_(2))nanosheet catalyst that exhibits improved activity and stability through a synergistic effect of Pd modulation of Ru electronic structure and the two-dimensional structure.The catalyst exhibits excellent performance,achieving an overpotential of only 204 mVat a current density of 10 mA cm^(-2).Impressively,after undergoing 8000 cycles of cyclic voltammetry testing,the overpotential merely decreased by 5 mV.The PEM electrolyzer with Pd0.08Ru0.92O_(2) as an anode catalyst survived an almost 130 h operation at 200 mA cm^(-2).To elucidate the underlying mechanisms responsible for the enhanced stability,we conducted an X-ray photoelectron spectroscopy(XPS)analysis,which reveals that the electron transfer from Pd to Ru effectively circumvents the over-oxidation of Ru,thus playing a crucial role in enhancing the catalyst's stability.Furthermore,density functional theory(DFT)calculations provide compelling evidence that the introduction of Pd into RuO_(2) effectively modulates electron correlations and facilitates the electron transfer from Pd to Ru,thereby preventing the overoxidation of Ru.Additionally,the application of the two-dimensional structure effectively inhibited the aggregation and growth of nanoparticles,further bolstering the structural integrity of the catalyst.
基金Funded by the National Natural Science Foundation of China (Nos.51772033, 52002040)the National Key Research and Development Program of China (No. 2023YFB3711400)。
文摘The purpose of this research is to investigate the hydration behavior and cementitious properties of the mixture of calcium carbonate and aluminate, and to explore whether it can be adopted as a new low-carbon cementitious material. The composite system of calcium carbonate and aluminate minerals is studied by measuring the component of hydration products, the hydration heat, setting time and compressive strength.The results prove that the composite system has certain cementitious properties and is feasible to prepare new low-carbon cement.
基金This work was supported by the National Natural Science Foundation of China(No.52004044)the Natural Science Foundation of Chongqing,China(Nos.cstb2022nscqmsx0801 and cstc2021jcyj-msxmx0882)+2 种基金the Foundation of Chongqing University of Science and Technology(No.ckrc2022030)the Graduate Research Innovation Project of Chongqing University of Science and Technology(No.YKJCX2220216)the National Undergraduate Training Program for Innovation and Entrepreneurship(No.202311551007).
文摘High-temperature oxidation behavior of ferrovanadium(FeV_(2)O_(4))and ferrochrome(FeCr_(2)O_(4))spinels is crucial for the application of spinel as an energy material,as well as for the clean usage of high-chromium vanadium slag.Herein,the nonisothermal oxidation behavior of FeV_(2)O_(4)and FeCr_(2)O_(4)prepared by high-temperature solid-state reaction was examined by thermogravimetry and X-ray diffraction(XRD)at heating rates of 5,10,and 15 K/min.The apparent activation energy was determined by the Kissinger-Akahira-Sunose(KAS)method,whereas the mechanism function was elucidated by the Malek method.Moreover,in-situ XRD was conducted to deduce the phase transformation of the oxidation mechanism for FeV_(2)O_(4)and FeCr_(2)O_(4).The results reveal a gradual increase in the overall apparent activation energies for FeV_(2)O_(4)and FeCr_(2)O_(4)during oxidation.Four stages of the oxidation process are observed based on the oxidation conversion rate of each compound.The oxidation mechanisms of FeV_(2)O_(4)and FeCr_(2)O_(4)are complex and have distinct mechanisms.In particular,the chemical reaction controls the entire oxidation process for FeV_(2)O_(4),whereas that for FeCr_(2)O_(4)transitions from a three-dimensional diffusion model to a chemical reaction model.According to the in-situ XRD results,numerous intermediate products are observed during the oxidation process of both compounds,eventually resulting in the final products FeVO_(4)and V2O_(5)for FeV_(2)O_(4)and Fe_(2)O_(3)and Cr_(2)O_(3)for FeCr_(2)O_(4),respectively.
基金financially supported by the Natural Science Foundation of Shandong Province (ZR2020QB132,ZR2020MB025)the Opening Project of State Key Laboratory of High Performance Ceramics and Superfine Microstructure (SKL202108SIC)the Taishan Scholar Program of Shandong Province (ts201712046)。
文摘Combination of CO_(2) capture using inorganic alkali with subsequently electrochemical conversion of the resultant HCO_(3)^(-)to high-value chemicals is a promising route of low cost and high efficiency.The electrochemical reduction of HCO_(3)^(-)is challenging due to the inaccessible of negatively charged molecular groups to the electrode surface.Herein,we adopt a comprehensive strategy to tackle this challenge,i.e.,cascade of in situ chemical conversion of HCO_(3)^(-)to CO_(2) and CO_(2) electrochemical reduction in a flow cell.With a tailored Ni-N-S single atom catalyst(SACs),where sulfur(S)atoms located in the second shell of Ni center,the CO_(2)electroreduction(CO_(2)ER)to CO is boosted.The experimental results and density functional theory(DFT)calculations reveal that the introduction of S increases the p electron density of N atoms near Ni atom,thereby stabilizing^(*)H over N and boosting the first proton coupled electron transfer process of CO_(2)ER,i.e.,^(*)+e^(-)+^(*)H+^(*)CO_(2)→^(*)COOH.As a result,the obtained catalyst exhibits a high faradaic efficiency(FE_(CO)~98%)and a low overpotential of 425 mV for CO production as well as a superior turnover frequency(TOF)of 47397 h^(-1),outcompeting most of the reported Ni SACs.More importantly,an extremely high FECOof 90%is achieved at 50 mA cm^(-2)in the designed membrane electrode assembly(MEA)cascade electrolyzer fed with liquid bicarbonate.This work not only highlights the significant role of the second coordination on the first coordination shell of the central metal for CO_(2)ER,but also provides an alternative and feasible strategy to realize the electrochemical conversion of HCO_(3)^(-)to high-value chemicals.
基金supported by the National Natural Science Foundation of China(Grant No.52071276)the Natural Science Foundation of Chongqing,China(Grant No.CSTB2022NSCQ-MSX0440)the Fundamental Research Funds for the Central Universities(Grant No.SWUXDJH202313,SWU-KQ22083).
文摘Mg-based amorphous alloys exhibit efficient catalytic performance and excellent biocompatibility with a promising application probability,specifically in the field of azo dye wastewater degradation.However,the problems like difficulty in preparation and poor cycling stability need to be solved.At present,Mg-based amorphous alloys applied in wastewater degradation are available in powder and ribbon.The amorphous alloy powder fabricated by ball milling has a high specific surface area,and its reactivity is thousands of times better than that of gas atomized alloy powder.But the development is limited due to the high energy consumption,difficult and costly process of powder recycling.The single roller melt-spinning method is a new manufacturing process of amorphous alloy ribbon.Compared to amorphous powder,the specific surface area of amorphous ribbon is relatively lower,therefore,it is necessary to carry out surface modification to enhance it.Dealloying is a way that can form a pore structure on the surface of the amorphous alloys,increasing the specific surface area and providing more reactive sites,which all contribute to the catalytic performance.Exploring the optimal conditions for Mg-based amorphous alloys in wastewater degradation by adjusting amorphous alloy composition,choosing suitable method to preparation and surface modification,reducing cost,expanding the pH range will advance the steps to put Mg-based amorphous alloys in industrial environments into practice.
基金supported by the National Natural Science Foundation of China(11872171 and 22209037)the Project on Excellent Post-graduate Dissertation of Hohai University。
文摘Although metallic rhodium(Rh)is regarded as a promising platinum-alternative anode catalyst of direct methanol fuel cell(DMFC),the conventional"particle-to-face"contact model between Rh and matrix largely limits the overall electrocatalytic performance due to their insufficient cooperative effects.Herein,we report a controllable and robust heterointerface engineering strategy for the bottom-up fabrication of rhombic Rh nanosheets in situ confined on Ti_3C_(2)T_x MXene nanolamellas(Rh NS/MXene)via a convenient stereoassembly process.This unique design concept gives the resulting 2D/2D Rh NS/MXene heterostructure intriguing textural features,including large accessible surface areas,strong"face-toface"interfacial interactions,homogeneous Rh nanosheet distribution,ameliorative electronic structure,and high electronic conductivity.As a consequence,the as-prepared Rh NS/MXene nanoarchitectures exhibit exceptional electrocatalytic methanol oxidation properties in terms of a large electrochemically active surface area of 126.2 m~2 g_(Rh)~(-1),a high mass activity of 1056.9 mA mg_(Rh)-~1,and a long service life,which significantly outperform those of conventional particle-shaped Rh catalysts supported by carbon black,carbon nanotubes,reduced graphene oxide,and MXene matrixes as well as the commercial Pt nanoparticle/carbon black and Pd nanoparticle/carbon black catalysts with the same noble metal loading amount.Density functional theory calculations further demonstrate that the direct electronic interaction at the well-contacted 2D/2D heterointerfaces effectively enhances the adsorption energy of Rh nanosheets and induces a left shift of the d-band center,thereby making the Rh NS/MXene configuration suffer less from CO poisoning.This work highlights the importance of rational heterointerface design in the construction of advanced noble metal/MXene electrocatalysts,which may provide new avenues for developing the next-generation DMFC devices.
基金supported by key technology research and development project of Shan Xi province(20201102019)Natural science foundation of Shanxi Province(201901D111167)+1 种基金Shanxi Scholarship Council of China(2020–117)JCKY2018408B003Magnesium alloy high-performance XXX multi-directional extrusion technology and XX supporting scientific research project(xxxx-2019-021)。
文摘The extruded AZ80+0.4%Ce magnesium alloy was twisted in the temperature range of 300-380℃by using a Gleeble 3500 thermal simulation test machine with a torsion unit.The deformed cylindrical specimens were cooled at a cooling rate of 10℃/s or 0.1℃/s,respectively,and aged at 170℃.The microstructure analysis results showed that the grain size decreased with increasing specimen radial position from center(SRPC),and that the strong initial basal texture of the extruded magnesium alloy was weakened.Both continuous and discontinuous dynamic recrystallization mechanisms were involved in contributing to the grain refinement for all specimens investigated.And a novel extension twinning induced dynamic recrystallization mechanism was proposed for specimen deformed at 300℃.For the specimens deformed at 300℃and 340℃followed by a slow cooling rate(0.1℃/s),precipitates of various shapes(β-Mg_(17)Al_(12)),with the dominant precipitates being on the grains boundaries,appeared on the surface section.For specimen deformed at 380℃,lamellar precipitates(LPS)in the interiors of the grains were predominant.After aging,the LPS still dominated for specimens twisted at 380℃;however,the LPS gradually decreased with decreasing deformation temperatures from 380℃to 300℃.Dynamically precipitatedβ,especially those decorating the grain boundaries,changed the competition pictures for the LPS and precipitates of other shapes after aging.Interestingly,LPS dominated the areas for the center section of the specimens after aging regardless of deformation temperatures.Low temperature deformation with high SRPC followed by rapid cooling rate increased the micro hardness of the alloy after aging due to refined grain,reduced precipitates size,decreased lamellar spacing as well as strain hardening.
基金This work was financially supported by the National Natural Science Foundation of China(22075171)Natural Science Foundation of Shanghai(23ZR1423400)The firstprinciples calculations were supported by the High Performance Computing Center of Shanghai University.
文摘Hydrogen evolution reaction(HER)has become a key factor affecting the cycling stability of aqueous Zn-ion batteries,while the corresponding fundamental issues involving HER are still unclear.Herein,the reaction mechanisms of HER on various crystalline surfaces have been investigated by first-principle calculations based on density functional theory.It is found that the Volmer step is the ratelimiting step of HER on the Zn(002)and(100)surfaces,while,the reaction rates of HER on the Zn(101),(102)and(103)surfaces are determined by the Tafel step.Moreover,the correlation between HER activity and the generalized coordination number(CN)of Zn at the surfaces has been revealed.The relatively weaker HER activity on Zn(002)surface can be attributed to the higher CN of surface Zn atom.The atomically uneven Zn(002)surface shows significantly higher HER activity than the flat Zn(002)surface as the CN of the surface Zn atom is lowered.The CN of surface Zn atom is proposed as a key descriptor of HER activity.Tuning the CN of surface Zn atom would be a vital strategy to inhibit HER on the Zn anode surface based on the presented theoretical studies.Furthermore,this work provides a theoretical basis for the in-depth understanding of HER on the Zn surface.